KR20060128009A - Substituted sym-triindole - Google Patents

Abstract

Novel substituted sym-triindole derivative that is applicable to a wide spectrum of uses, such as various electrification preventions, electrification controls, capacitors, batteries, chemical sensors, displays, organic EL materials, solar cells, photodiodes, phototransistors, nonlinear materials, photorefractive materials, rustproof agents, adhesives, fibers, antistatic paints, electrodeposition paints, plating primers, electric protections, etc. There is provided a substituted sym-triindole derivative of the general formula: (1) (wherein each of R1, R2, R3 and R4 independently represents hydrogen, a halogen, a C1- C6 alkyl, etc, provided that in no event all of R1, R2, R3 and R4 are simultaneously hydrogens).

Description

Substituted Sxym-triindole {SUBSTITUTED SYM-TRIINDOLE}

The present invention provides a novel substituted Sym-triindole derivative and a method for producing the same. Substituted Sym-triindole derivatives of the present invention are antistatic, antistatic, capacitors, batteries, chemical sensors, display elements, organic EL materials, solar cells, photodiodes, phototransistors, nonlinear materials, photoreflectors. It can be widely applied to creative materials, rust preventives, adhesives, fibers, antistatic paints, electrodeposition paints, plating primers, and electrocorrosion.

Although bisubstituted derivatives of Sym-triindole derivatives have been reported, the synthesis of the tri-substituted Sym-triindole derivatives with trisubstitution or more is difficult (see Patent Document 1).

Patent Document 1: Japanese Patent Application Laid-Open No. 2000-105139

[Problem to Solve Invention]

The present invention provides various antistatic, antistatic, capacitor, battery, chemical sensor, display element, organic EL material, solar cell, photodiode, phototransistor, nonlinear material, photoreflective material, rust inhibitor, adhesive, fiber, antistatic An object of the present invention is to provide a novel substituted Sym-triindole derivative which can be widely applied to paints, electrodeposition paints, plating primers, electrical systems, and the like.

[Means for solving the problem]

In view of the above circumstances, the present inventors have intensively studied a method for producing a substituted Sym-triindole derivative, and surprisingly, by reacting phosphorus oxyhalogenated compounds such as substituted oxyindoles with phosphorus oxychloride, 3 The inventors have found that the Sym-triindole derivatives of substitution or more can be selectively synthesized, that is, the above problems can be solved, and the present invention has been completed based on this finding.

[Effects of the Invention]

By the method of the present invention, various antistatic, antistatic, capacitors, batteries, chemical sensors, display elements, organic EL materials, solar cells, photodiodes, phototransistors, nonlinear materials, photoreflective materials, rust inhibitors, adhesives, fibers There is provided a novel substituted Sym-triindole derivative, which can be widely applied to antistatic paints, electrodeposition paints, plating primers, electrical systems, and the like.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. This invention provides the invention as described in following [1]-[14].

[1] General formula (1)

[Formula 1]

(In formula, R <_1> , R <_2> , R <_3> , R <_4> is respectively independently hydrogen, halogen, C1-C6 alkyl group, C1-C6 haloalkyl group, substituted C1-C6 alkyl group, C2-C6 alkenyl group, substituted C2- C6 alkenyl group, C2-C6 alkynyl group, substituted C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, aryloxy group, amino group, monosubstituted amino group, disubstituted amino group, acylamino group, mercapto group, C1- C6 alkylsulphenyl group, C1-C6 haloalkylsulphenyl group, arylsulphenyl group, substituted arylsulphenyl group, C1-C6 alkylsulfinyl group, C1-C6 haloalkylsulfinyl group, aralkylsulphenyl group, arylsulfinyl group, substituted arylsulfinyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylsulfonyl group, arylsulfonyl group, substituted arylsulfonyl group, sulfonic acid group (hydroxysulfonyl group), aryl group, substituted aryl group, cyano group, nitro group, formyl group, Acyl group, carboxyl group, C1-C6 alkoxycarbonyl group, carbamoyl group, N-monosubstituted carbamoyl group, N, N-disubstituted carbamoyl group, hydrazonomethyl group (-CH = N-NH ₂ group), N-mono substituted hydrazonomethyl group, N, N-disubstituted hydrazonomethyl group, an oxime methyl group (hydroxyiminomethyl group), C1-C6 alkoxy iminomethyl group, an aryloxy iminomethyl group, R ₅ Represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group, provided that R ₁ , R ₂ , R ₃ , and R ₄ are not all hydrogen at the same time. )

Substituted Sym-triindole derivative, characterized in that.

[2] General formula (2)

[Formula 2]

(In formula, R <_1> , R <_2> , R <_3> , R <_4> is respectively independently hydrogen, halogen, C1-C6 alkyl group, C1-C6 haloalkyl group, substituted C1-C6 alkyl group, C2-C6 alkenyl group, substituted C2- C6 alkenyl group, C2-C6 alkynyl group, substituted C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, aryloxy group, amino group, monosubstituted amino group, disubstituted amino group, acylamino group, mercapto group, C1- C6 alkylsulphenyl group, C1-C6 haloalkylsulphenyl group, aralkylsulphenyl group, arylsulphenyl group, substituted arylsulphenyl group, C1-C6 alkylsulfinyl group, C1-C6 haloalkylsulfinyl group, arylsulfinyl group, substituted arylsulfinyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylsulfonyl group, arylsulfonyl group, substituted arylsulfonyl group, sulfonic acid group (hydroxysulfonyl group), aryl group, substituted aryl group, cyano group, nitro group, formyl group, Acyl group, carboxyl group, C1-C6 alkoxycarbonyl group, carbamoyl group, N-monosubstituted carbamoyl group, N, N-disubstituted carbamoyl group, hydrazonomethyl group (-CH = N-NH ₂ group), N-mono substituted hydrazonomethyl group, N, N-disubstituted hydrazonomethyl group, an oxime methyl group (hydroxyiminomethyl group), C1-C6 alkoxy iminomethyl group, an aryloxy iminomethyl group, R ₅ Represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group, provided that R ₁ , R ₂ , R ₃ , and R ₄ are not all hydrogen at the same time. )

General formula (1) characterized by reacting substituted oxyindole represented by phosphorus oxyhalogenated with

[Formula 3]

(Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ represent the same meanings as above).

Method for producing a substituted Sym-triindole derivative represented by.

[3] General formula (3)

[Formula 4]

(Wherein R ₅ represents C2-C12 alkyl group, substituted C2-C12 alkyl group, C2-C12 haloalkyl group, arylC1-C6 alkyl group, R ₆ represents hydrogen, formyl group, cyano group, C1-C6 alkoxycarbonyl group, dicyano A vinyl group, an aryl group, or a substituted aryl group.)

Sym-triindole derivative, characterized in that represented by.

[4] General formula (4)

[Formula 5]

(Wherein R ₅ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, an aryl C1-C6 alkyl group, and X represents a halogen.)

N-substituted-5-halo-oxyindole represented by the following reaction with phosphorus oxyhalogenated compound, formula (5)

[Formula 6]

(Wherein R ₅ and X have the same meaning as above).

To obtain an N-substituted-5-halo-triindole derivative represented by the formula (6).

[Formula 7]

(Wherein R ₇ represents hydrogen, formyl group, cyano group, C1-C6 alkoxycarbonyl group, aryl group or substituted aryl group, and R _a , R _b may each independently have a hydrogen atom, a C1-C6 alkyl group or a substituent) A phenyl group, and R _a and R _b may be bonded to each other to form a ring;

A general formula (7) characterized by reacting with a boric acid compound represented by

[Formula 8]

(Wherein R ₅ and R ₇ have the same meaning as above).

Method for producing a Sym- triindole derivative represented by.

[5] General formula (5)

[Formula 9]

(Wherein R ₅ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, an arylC1-C6 alkyl group, and X represents a halogen.)

N-substituted-5-halo-triindole derivatives represented by the general formula (6)

[Formula 10]

(Wherein R ₇ represents hydrogen, formyl group, cyano group, C1-C6 alkoxycarbonyl group, aryl group or substituted aryl group, and R _a , R _b may each independently have a hydrogen atom, a C1-C6 alkyl group or a substituent) It may represent a phenyl group, and R _a and R _b may combine to form a ring.)

A general formula (7) characterized by reacting with a boric acid compound represented by

[Formula 11]

(Wherein R ₅ and R ₇ have the same meaning as above).

Method for producing a Sym- triindole derivative represented by.

[6] General formula (4)

[Formula 12]

(Wherein R ₅ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, an aryl C1-C6 alkyl group, and X represents a halogen.)

Formula (5), characterized by reacting N-substituted-5-halo-oxyindole represented with phosphorus oxyhalogenated with

[Formula 13]

(Wherein R ₅ and X have the same meaning as above).

Method for producing an N-substituted-5-halo-triindole derivative represented by

[7] General formula (8)

[Formula 14]

(In formula, R <_5> represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, and an aryl C1-C6 alkyl group.)

Triindole derivatives represented by the general formula (9)

[Formula 15]

(Wherein R ₈ represents hydrogen or a cyano group, and R ₉ represents a cyano group, a carboxylic acid group, a C1-C6 alkoxycarbonyl group, an aryl group, a substituted aryl group.)

Reacting with a methylene compound represented by the general formula (10)

[Formula 16]

(Wherein R ₅ , R ₈ and R ₉ represent the same meaning as above).

Method for producing a Sym- triindole derivative represented by.

[8] General formula (11)

[Formula 17]

(Wherein R ₈ represents hydrogen or cyano group, R ₉ represents cyano group, carboxylic acid group, C1-C6 alkoxycarbonyl group, aryl group, or substituted aryl group, R ₁₀ is C2-C12 alkyl group, substituted C2-C12 An alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group.)

Sym-triindolevinyl derivative, characterized in that represented by.

[9] General formula (12)

[Formula 18]

(Wherein R ₁₀ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group, and X represents a halogen.)

The oxyindole compound represented by the reaction is reacted with phosphorus oxyhalogenated compound to formula (13)

[Formula 19]

(Wherein R ₁₀ and X have the same meaning as above).

To obtain a Sym-halo-triindole derivative represented by the following, formylated with a formylating agent in the presence of butyllithium,

[Formula 20]

(Wherein R ₁₀ represents the same meaning as above).

To obtain a Sym- formyl triindole derivative represented by the general formula (9)

[Formula 21]

(Wherein R ₈ represents hydrogen or a cyano group, and R ₉ represents a cyano group, a carboxylic acid group, a C1-C6 alkoxycarbonyl group, an aryl group, a substituted aryl group.)

Reacting with a methylene compound represented by the general formula (11)

[Formula 22]

(In formula, R <_8> , R <_9> , R <_10> shows the same meaning as the above.)

Method for producing a Sym- triindole derivative represented by.

[10] General Formula (14)

[Formula 23]

(Wherein R ₁₀ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group.)

Sym-formyltriindole derivatives represented by the general formula (9)

[Formula 24]

(Wherein R ₈ represents hydrogen or a cyano group, and R ₉ represents a cyano group, a carboxylic acid group, a C1-C6 alkoxycarbonyl group, an aryl group, a substituted aryl group.)

Reacting with a methylene compound represented by the general formula (11)

[Formula 25]

(In formula, R <_8> , R <_9> , R <_10> shows the same meaning as the above.)

Method for producing a Sym- triindole derivative represented by.

[11] General formula (13)

[Formula 26]

(Wherein R ₁₀ represents a C2-C12 alkyl group, a C2-C12 substituted alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group, and X represents a halogen.)

Formula (14), characterized in that formylation is carried out with a formylating agent in the presence of butyllithium to a Sym-halo-triindole derivative represented by

[Formula 27]

(Wherein R ₁₀ represents the same meaning as above).

Method for producing a Sym- formyl triindole derivative represented by.

[12] General formula (15)

[Formula 28]

(Wherein R ₁₀ represents a C2-C12 alkyl group, a C2-C12 substituted alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group, and R ₁₁ represents an aryl group or a substituted aryl group.)

Sym-triindole derivative, characterized in that represented by.

[13] General formula (13)

[Formula 29]

(Wherein R ₁₀ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group, and X represents a halogen.)

Sym-halo-triindole derivatives represented by the general formula (16)

[Formula 30]

(Wherein R ₁₁ represents an aryl group or a substituted aryl group, and R ₁₂ represents a hydrogen or trimethylsilyl group.)

Reacting with an acetylene derivative represented by the general formula (15)

[Formula 31]

(In formula, R <_10> , R <_11> shows the same meaning as the above.)

Method for producing a Sym- triindole derivative represented by.

[14] General Formula (13)

(Wherein R ₁₀ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group, and X represents a halogen.)

Sym-halo-triindole derivative, characterized in that represented by.

Terms used in the present specification will be described.

The expression "C1-C6" or the like indicates that the carbon number of the group following this is 1 to 6 in this case.

"Halogen" represents fluorine, chlorine, bromine or iodine.

"C1-C6 alkyl group" refers to a linear or branched C1-C6 alkyl group having 1 to 6 carbon atoms, and specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl Group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, 3,3-dimethylbutyl group, etc. can be illustrated.

"C2-C12 alkyl group" refers to a straight or branched C2-C12 alkyl group having 2 to 12 carbon atoms, and specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl Group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, 3,3-dimethylbutyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-decyl group , n-dodecyl group, etc. can be illustrated.

The "aryl group" refers to an aromatic group which may include a heterocyclic atom, a 5- or 6-membered monocyclic ring, or a condensed ring optionally bonded by a 5-membered ring and / or a 6-membered ring, for example, a phenyl group , 1-naphthyl group, 2-naphthyl group, 1-anthranyl group, 2-anthranyl group, 9-anthranyl group, 1-phenanthryl group, 2-phenanthryl group, 9-phenanthryl group, 3-phenanthryl group, Monocyclic or condensed cyclic aromatic hydrocarbon groups such as 4-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group, and 4-pyrenyl group; Or 2-pyridyl group, 3-pyridyl group, pyrrole group, pyrazolyl group, triazolyl group, quinolinyl group, indolyl group, isoindolyl group, thienyl group, benzothienyl group, furyl group, phenzofuryl group, thia One or more nitrogen, oxygen, sulfur as a binary atom, such as a zolyl group, an oxiazolyl group, a benzothiazolyl group, an oxazolyl group, an isoxoxazolyl group, a benzooxazolyl group, a thiadiazolyl group or a benzothiadiazolyl group The monocyclic or condensed ring aromatic heterocyclic group which has the following can be illustrated.

A "substituted aryl group" represents the aryl group which has the said meaning substituted by 1-7 of halogen, cyano group, formyl group, and aryl group which have the said meaning, for example 2-chlorophenyl group and 4-sia Nophenyl group, 4-formylphenyl group, 2-phenyl-1,3,4-oxadiazole-5-yl group, 2- (4-n-butylphenyl) -1,3,4-oxadiazole-5- Diary, 2- (4-t-butylphenyl) -1,3,4-oxadiazole-5-yl group, 2- (4-n-hexylphenyl) -1,3,4-oxadiazole-5- Diary etc. can be illustrated.

"C1-C6 alkoxy group" means "(C1-C6 alkyl) -O- group having the above meaning", for example, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n- Butoxy group, tert- butoxy group, n-pentyloxy group, n-hexyloxy group, etc. can be illustrated.

A C1-C6 alkoxycarbonyl group represents "(C1-C6 alkoxy) -CO- group having the above meaning", for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc. can be illustrated.

"Aryloxy group" represents "(aryl) -O- group with the said meaning", for example, phenoxy etc. can be illustrated.

"C1-C6 haloalkyl group" refers to a straight or branched C1-C6 alkyl group substituted with 1 to 13 of the same or different halogen having the above meaning, for example, chloromethyl group, dichloromethyl group, trichloromethyl group, tri Fluoromethyl group etc. can be illustrated.

The "C2-C12 haloalkyl group" refers to a straight or branched C2 to C12 alkyl group substituted with 1 to 13 of halogen having the same or different meanings, for example, a chloroethyl group, 1,1-dichloroethyl group, 2 A 2, 2- trichloroethyl group, a 2, 2, 2- trifluoroethyl group, etc. can be illustrated.

The "substituted C1-C6 alkyl group" refers to a straight or branched C1-C6 alkyl group substituted with 1 to 13 of the same or different hydroxy groups, C1 to C6 alkoxy groups having the above meanings, and aryl groups having the above meanings. For example, a hydroxymethyl group, a methoxymethyl group, and a phenylethyl group can be illustrated.

The "substituted C2-C12 alkyl group" refers to a hydroxy group having the same meaning or different and a straight or branched C2-C12 alkyl group substituted with 1 to 13 of the C1-C6 alkoxy group having the above meaning, for example, A hydroxyethyl group and a methoxyethyl group can be illustrated.

The "aryl C1-C6 alkyl group" refers to a straight or branched C2-C12 alkyl group substituted with 1 to 13 of the same or different aryl groups having the above meaning, and examples thereof include benzyl groups, phenylethyl groups, and the like. Can be.

"C2-C6 alkenyl group" represents a linear or branched C2-C6 alkenyl group, and examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, and the like.

The "carboxyl group" refers to a carboxyl group or a carboxyl group forming a salt. For example, carboxylic acid (-COOH), sodium carbonate (-COONa), potassium carbonate (-COOK), lithium carbonate (-COOLi), Groups, such as a pyridinium carboxylate (-COOH * Pyridine), can be illustrated.

The "substituted C2-C6 alkenyl group" is the same or different, the cyano group having the above meaning, the carboxylic acid group having the above meaning, the C1-C6 alkoxycarbonyl group having the above meaning, the aryl group having the above meaning, and the above meaning Linear or branched C2 to C6 alkenyl group substituted with 1 to 11 of the substituted aryl group having, for example, 2,2-dicyanovinyl group, (2-cyano-2-ethoxycarbonyl) vinyl group , (2-cyano-2-carboxy) vinyl group, (2-cyano-2-phenyl) vinyl group, (2-cyano-2- (4-nitrophenyl)) vinyl group, (2-cyano A 2- (4-pyridyl)) vinyl group etc. can be illustrated.

"C2-C6 alkynyl group" represents a straight-chain or branched C2-C6 alkynyl group, for example, an ethynyl group, a 1-propynyl group, a 1-butynyl group, etc. can be illustrated.

The "substituted C2-C6 alkynyl group" refers to a straight-chain or branched C2-C6 alkynyl group substituted with 1 to 9 of the aryl group having the above meaning, for example, a phenylethynyl group, (4-pyridyl) ethynyl Etc. can be illustrated.

"Acyl group" means "(C1-C6 alkyl) -CO- group having the above meaning", "(C1-C6 haloalkyl) -CO- group having the above meaning", "(aryl having the above meaning)- CO-group "or" (substituted aryl) -CO-group having the above meaning ", for example, an acetyl group, propionyl group, benzoyl group, etc. can be illustrated.

A "monosubstituted amino group" represents the C1-C6 alkyl group which has the said meaning, or the amino group monosubstituted by the aryl group which has the said meaning, For example, a methylamino group, an ethylamino group, a phenylamino group, etc. can be illustrated.

The "disubstituted amino group" refers to an amino group di-substituted with the same or different C1-C6 alkyl group having the above meaning or an aryl group having the above meaning, and examples thereof include dimethylamino group, diethylamino group, diphenylamino group and the like. can do.

The "acylamino group" represents an amino group monosubstituted with a C1-C6 acyl group having the above meaning, and examples thereof include an acetylamino group, propionylamino group, butyrylamino group, and the like.

"C1-C6 alkylsulphenyl group" means "(C1-C6 alkyl) -S- group having the above meaning", for example, methylsulphenyl group (methylthio group) and ethylsulphenyl group (ethylthio group) It can be illustrated.

"Arylsulphenyl group" represents "(aryl) -S-group which has the said meaning", For example, a phenylsulphenyl group (phenylthio group) can be illustrated.

A "substituted aryl sulfenyl group" means "(substituted aryl) -S-group" with the said meaning, For example, a (4-chlorophenyl) sulfenyl group ((4-chlorophenyl) thio group) can be illustrated. have.

"C1-C6 haloalkylsulphenyl group" means "(C1-C6 haloalkyl) -S- group having the above meaning", for example, trifluoromethylsulphenyl group (trifluoromethylthio group), etc. It can be illustrated.

"Aralkyl sulfenyl group" means "(aryl having the above meaning)-(alkyl having the above meaning) -S- group" or "(substituted aryl having the above meaning)-(alkyl having the above meaning) -S- Group ”, for example, a benzyl sulfenyl group (benzylthio group), a (4-chloropenzyl) sulfenyl group ((4-chlorobenzyl) thio group), etc. can be illustrated.

"C1-C6 alkylsulfinyl group" means "(C1-C6 alkyl) -SO- group" having the above meaning, and examples thereof include methylsulfinyl, ethylsulfinyl, and the like.

"C1-C6 haloalkylsulfinyl group" means "(C1-C6 haloalkyl) -SO- group" having the above meaning, for example, trifluoromethylsulfinyl group, chloromethylsulfinyl group, 2-chloroethyl A sulfinyl group etc. can be illustrated.

"Arylsulfinyl group" shows "(aryl) -SO- group which has the said meaning", For example, a phenylsulfinyl group etc. can be illustrated.

A "substituted aryl sulfenyl group" shows "(substituted aryl) -SO- group which has the said meaning", For example, 4-chlorophenyl sulfinyl group etc. can be illustrated.

"C1-C6 alkylsulfonyl group" represents "(C1-C6 alkyl) -SO ₂ -group having the above meaning", and examples thereof include a methanesulfonyl group and an ethanesulfonyl group.

"C1-C6 haloalkylsulfonyl group" means "(C1-C6 haloalkyl) -SO ₂ -group having the above meaning", for example, trifluoromethanesulfonyl group, chloromethanesulfonyl group, 2-chloro An ethane sulfonyl group etc. can be illustrated.

"Arylsulfonyl group" means, "(aryl having the above meaning) -SO ₂ - group" refers to, for example, there can be mentioned a phenyl sulfonyl.

The "substituted arylsulfonyl group" represents "(substituted aryl) -SO ₂ -group having the above meaning", and examples thereof include (4-chlorophenyl) sulfonyl and the like.

A "sulfonic acid group" represents a -SO ₂ -OH group.

The "N-monosubstituted carbamoyl group" refers to a C1-C6 alkyl group having the above meaning or a carbamoyl group in which a nitrogen atom is monosubstituted with an aryl group having the above meaning, for example, methyl carbamoyl group, phenyl carbamoyl group or the like. Can be illustrated.

The "N, N-disubstituted carbamoyl group" refers to a C1-C6 alkyl group having the above meaning or a carbamoyl group in which a nitrogen atom is disubstituted with an aryl group having the above meaning, for example, a dimethylcarbamoyl group or a diphenylcarba A grouping group etc. can be illustrated.

A "hydrazonomethyl group" represents a -CH = N-NH ₂ group.

The "N-monosubstituted hydrazonomethyl group" refers to a C1-C6 alkyl group having the above meaning or a hydrazonomethyl group in which a nitrogen atom is monosubstituted with an aryl group having the above meaning, for example, a methylhydrazonomethyl group, a phenylhydrazonomethyl group, or the like. Can be illustrated.

The N, N-disubstituted hydrazonomethyl group refers to a C1-C6 alkyl group having the above meaning or a hydrazonomethyl group having a nitrogen atom disubstituted with an aryl group having the above meaning, for example, a dimethylhydrazonomethyl group or a diphenylhydrazonomethyl group. Etc. can be illustrated.

An "oxime methyl group (hydroxyiminomethyl group)" represents a -CH = N-OH group. "C1-C6 alkoxyiminomethyl group" represents the oxyiminomethyl group in which the oxygen atom was substituted by the C1-C6 alkyl group which has the said meaning, For example, a methoxy iminomethyl group, an ethoxy iminomethyl group, etc. can be illustrated.

The "aryloxyiminomethyl group" refers to an oxyiminomethyl group in which an oxygen atom is substituted with an aryl group having the above meaning, and examples thereof include phenoxyiminomethyl group.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

This invention [1] is a Sym- triindole derivative represented by General formula (1). R <_1> , R <_2> , R <_3> , R <_4> in General formula (1) may be same or different, and is each independently hydrogen, halogen, a halogen, a C1-C6 alkyl group, a C1-C6 haloalkyl group, and a substituted C1-C6. Alkyl group, C2-C6 alkenyl group, substituted C2-C6 alkenyl group, C2-C6 alkynyl group, substituted C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, aryloxy group, amino group, monosubstituted amino group, disubstituted Amino group, acylamino group, mercapto group, C1-C6 alkylsulphenyl group, C1-C6 haloalkylsulphenyl group, arylsulphenyl group, substituted arylsulphenyl group, C1-C6 alkylsulfinyl group, C1-C6 haloalkylsulfinyl group, aralkyl sulfide Phenyl group, arylsulfinyl group, substituted arylsulfinyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylsulfonyl group, arylsulfonyl group, substituted arylsulfonyl group, sulfonic acid group (hydroxysulfonyl group), aryl group, substituted aryl Group, cyano group, nitro group, formyl group, acyl group, carboxyl group, C1-C6 alkoxycarbonyl group, carbamoyl group, N-monosubstituted carbamoyl group , N, N-disubstituted carbamoyl group, hydrazonomethyl group (-CH = N-NH ₂ group), N-monosubstituted hydrazonomethyl group, N, N-disubstituted hydrazonomethyl group, oxime methyl group (hydroxyiminomethyl group ), A C1-C6 alkoxyiminomethyl group, an aryloxyiminomethyl group,

R <_5> represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, and an aryl C1-C6 alkyl group. However, R ₁ , R ₂ , R ₃ and R ₄ are not all hydrogen at the same time.

Therefore, as a compound of this invention, the compound listed in Table 1 can be illustrated. In addition, the symbol used in each table | surface in the following description shows the following meaning, respectively.

MeO: methoxy group

COOMe: methoxycarbonyl group

COOEt: Ethoxycarbonyl

Ph: phenyl group

NHBn: benzylamino group

SPh: Phenylsulphenyl group (phenylthio group)

SOPh: Phenylsulfinyl

SO ₂ Ph: phenylsulfonyl group

COMe: Acetyl group

CONHPh: Phenylcarbamoyl group

NHCOPh: Benzoylamino group

vinyl: vinyl

Et: ethyl group

n-Pr: n-propyl group

Bu: n-butyl group

Pen: n-pentyl group

n-Hex: n-hexyl group

(2-Et) HHex: 2-ethylhexyl group

Dicyano vinyl: 2, 2- dicyano vinyl group

Py: pyridyl

TMS-ethynyl: trimethylsilylethynyl group

[Formula 33]

TABLE 1

This invention [2] is a manufacturing method of the substituted Sym- triindole derivative represented by General formula (1) by making oxyindole represented by General formula (2), and phosphorus oxyhalogenation react.

First, the oxyindole represented by General formula (2) used as a raw material of this invention is demonstrated.

R <_1> , R <_2> , R <_3> , R <_4> in General formula (2) is respectively independent and may mutually be same or different, and each independently, hydrogen, a halogen, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a substituted C1- C6 alkyl group, C2-C6 alkenyl group, substituted C2-C6 alkenyl group, C2-C6 alkynyl group, substituted C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, aryloxy group, amino group, monosubstituted amino group, di Substituted amino group, acylamino group, mercapto group, C1-C6 alkylsulphenyl group, C1-C6 haloalkylsulphenyl group, aralkylsulphenyl group, arylsulphenyl group, substituted arylsulphenyl group, C1-C6 alkylsulfinyl group, C1-C6 haloalkyl Sulfinyl group, arylsulfinyl group, substituted arylsulfinyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylsulfonyl group, arylsulfonyl group, substituted arylsulfonyl group, sulfonic acid group (hydroxysulfonyl group), aryl group, substituted Aryl group, cyano group, nitro group, formyl group, acyl group, carboxyl group, C1-C6 alkoxycarbonyl group, carbamoyl group, N-monosubstituted car Parent group, N, N- di-substituted carbamoyl, hydra Hanazono group (-CH = N-NH ₂ group), N- mono-substituted hydrazine Hanazono methyl group, an N, N- di-substituted hydrazine Hanazono methyl group, an oxime group (hydroxyimino Minomethyl group), a C1-C6 alkoxyiminomethyl group, an aryloxyiminomethyl group, and R <_5> represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, and an aryl C1-C6 alkyl group. However, R ₁ , R ₂ , R ₃ and R ₄ are not all hydrogen at the same time.

As halogen in R <_1> -R <_4> in general formula (2), bromine is preferable from the balance of reactivity and industrial availability, and as R <_5> , a C2-C12 alkyl group is preferable, and n-hexyl group is especially And 2-ethylhexyl group is preferable.

Therefore, specifically, for example, N-ethyl-5-bromooxyindole, N-ethyl-6-bromooxyindole, N-ethyl-7-bromooxyindole, N can be used as the oxyindole which can be used for the reaction. -Ethyl-5,6-dibromooxyindole, N-ethyl-5,7-dibromooxyindole, N-ethyl-5-chlorooxyindole, N-ethyl-5-iodineoxyindole, N-propyl -5-bromooxyindole, N-iso-propyl-5-bromooxyindole, N- (n-hexyl) -5-bromooxyindole, N- (n-octyl) -5-bromooxyindole And N- (2-ethyl) hexyl-5-bromooxyindole, N- (n-hexyl) -5-methyloxyindole and the like.

Oxyindole used in the present invention is known, but can be produced by a method of reacting the corresponding aniline with chloroacetyl chloride in the presence of aluminum chloride.

As phosphorus oxyhalide, phosphorus oxychloride, phosphorus oxybromide, etc. can be illustrated, for example, Usually phosphorus oxychloride is used preferably.

The molar ratio of oxyindole used for the raw material to phosphorus oxyhalogenated may be any molar ratio as long as stirring is possible. Preferably, the molar ratio of 0.5-30L, preferably 1 to 10L is exemplified for 1 mole of oxyindole as the raw material can do.

The reaction temperature of the reaction may be any temperature as long as the reaction proceeds. Preferably, the range of the reflux temperature is preferably 80 ° C.

Although the reaction time of the said reaction is not specifically limited, Preferably it can illustrate from 1 hour to 48 hours.

In addition, the compound whose R <_1> , R <_2> , R <_3> , R <_4> is a hydrazonomethyl group, N-monosubstituted hydrazonomethyl group, and N, N-disubstituted hydrazonomethyl group is obtained as mentioned above, and R <_1> , R <_2> , N-monosubstituted hydrazine represented by C1-C6 alkylhydrazine, phenylhydrazine, etc., such as hydrazine, such as methyl hydrazine and ethyl hydrazine, in the compound whose R <_3> , R <_4> is a formyl group, for example, N, N It can manufacture by making N, N-disubstituted hydrazine represented by di (C1-C6 alkyl) hydrazine, such as -dimethyl hydrazine and N, N-diethyl hydrazine, diphenyl hydrazine, etc. react.

In addition, the compound whose R <_1> , R <_2> , R <_3> , and R <_4> is O-substituted oxyiminomethyl group, such as an oxime methyl group (hydroxyiminomethyl group), a C1-C6 alkoxyiminomethyl group, an aryloxyiminomethyl group, is carried out as mentioned above. obtained, R _1, R _2, R _3, by R ₄ is the reaction of hydroxylamine or its salt to the formyl group of the compound, or, R _1, R _2, R _3, R ₄ is formyl to push the compounds, for For example, C1-C6 alkoxyamine (alkanolamine), such as methoxyamine (methanolamine) or its salt, ethoxyamine (ethanolamine), or its salt, an aryloxyamine represented by its salt, phenoxyamine, etc. It can manufacture by making O-substituted oxyamine, such as these, react.

This invention [3] is a Sym- triindole derivative represented by General formula (3). R <_6> in General formula (4) is a hydrogen atom; formyl group; cyano group: dicyano vinyl group; For example, C1-C6 alkoxycarbonyl groups, such as a methoxycarbonyl, an ethoxycarbonyl, a propoxycarbonyl group; For example, an aryl group such as an oxadiazolyl group or 2-chlorophenyl group, 4-cyanophenyl group, 4-formylphenyl group, 2-phenyl-1,3,4-oxadiazole-5-yl group, 2- ( 4-n-butylphenyl) -1,3,4-oxadiazole-5-yl group, 2- (4-t-butylphenyl) -1,3,4-oxadiazole-5-yl group, 2- ( Substituted aryl groups, such as the 4-n-hexylphenyl) -1,3,4-oxadiazol-5-yl group, are shown.

Therefore, as a compound of this invention, the compound listed in Table 2 can be illustrated.

[Formula 34]

TABLE 2

Below, the absorption of light from the visible region to the ultraviolet region of Sym-N- (n-hexyl) -5- (4-formylphenyl) triindole (Formula 35), which is a typical compound exemplified by the present invention, The spectrum (FIG. 1), the fluorescence spectrum (FIG. 2: measured with dichloromethane solution, FIG. 3: measured in solid state) is illustrated.

[Formula 35]

It can be expected that the compound obtained in the present invention can be used for organic EL materials, solar cells and the like by having a fluorescence spectrum in the vicinity of 400 nm to 700 nm.

In this invention [4], N-substituted-5-halo-oxyindole represented by General formula (4) is made to react with phosphorus oxyhalogenation, and General formula (5)

[Formula 36]

(Wherein R ₅ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, an aryl C1-C6 alkyl group, and X represents a halogen.)

General formula (1) characterized by obtaining N-substituted-5-halo-triindole (first step), and further reacting the boric acid compound represented by the general formula (6) (second step). It is a method for producing a Sym-triindole derivative represented by.

First, the first step of the present invention will be described. This step is a step of reacting N-substituted-5-halo-oxyindole represented by General Formula (4) with phosphorus oxyhalogenated to produce N-substituted-5-halo-triindole.

Although the molar ratio of N-substituted-5-halo-oxyindole and phosphorus oxyhalogenide represented by General formula (4) used for the raw material of this process may be any molar ratio as long as stirring is possible, Preferably, the oxy of a raw material With respect to 1 mol of indoles, the range of 0.5-30 L, Preferably 1-10 L can be illustrated.

Although the reaction temperature of the said reaction will not be specifically limited if it is the temperature which reaction advances, Preferably, the range of reflux temperature can be illustrated from 80 degreeC.

Although the reaction time of the said reaction is not specifically limited, Preferably it can illustrate from 1 hour to 48 hours.

Next, the second step will be described. Step of reacting N-substituted-5-halo-oxyindole obtained in this step and all steps with a boric acid compound represented by the general formula (6) to produce a Sym-triindole derivative represented by the general formula (7). to be.

The boric acid compound represented by General formula (6) which is a raw material of this process is demonstrated. R <_6> in General formula (6) is a hydrogen atom; Formyl group; Cyano group; For example, C1-C6 alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl and iso-propoxycarbonyl are represented, and R _a and R _b are each independently a hydrogen atom or C1. -C6 alkyl group, or represents a phenyl group also get a substituent, R _a, R _b may also combine to form a ring. (Thus, R _a -BR _b is a boric acid group; for example, a straight-chain or branched C1-C12 alkylborate ester such as methoxyboric acid, ethoxyboric acid, iso-propoxyboric acid; 4,4,5,5- Cyclic boric acid esters such as tetramethyl-1,3,2-dioxaborolan-2-yl and 5,5-dimethyl-1,3,2-dioxaborox-2-yl.

Therefore, the boric acid compound represented by General formula (6) which can be used for the said reaction is specifically, for example, phenylboric acid, methyl phenyl borate, ethyl phenyl borate, isopropyl phenyl borate, 2-formylphenylboric acid, 3 -Formylphenylboric acid, 4-formylphenylboric acid, methyl4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate, ethyl4- (4,4,5,5-tetramethyl 1,3, 2-dioxaborolan-2-yl) benzoate, 4- (4,4,5,5-tetramethyl-1,3,2- Dioxaborolan-2-yl) benzonitrile, 4- (5,5-dimethyl-1,3,2-dioxaborox-2-yl) benzaldehyde, etc. can be illustrated.

Although the molar ratio of the boric acid compound represented by General formula (6) used for the said reaction and N-substituted-5-halo-triindole derivative reacts in any molar ratio, Preferably it is N-substituted-5-halo-triindole derivative 1 The range of 3-15 moles can be illustrated with respect to mole.

The reaction is performed using a solvent. As a solvent which can be used, if it does not inhibit this reaction, it will not be limited to use, Preferably, For example, aromatic hydrocarbons, such as benzene, toluene, xylene; For example, aprotic polar solvents such as dimethylformamide, diethylformamide and dimethylacetamide; For example, cyclic ethers, such as tetrahydrofuran (THF) and dioxane; For example, chain ethers, such as monolime and digrim; For example, Alcohol, such as methanol, ethanol, butanol, ethylene glycol, propylene glycol, PEG-400; Water and the like are used. The solvent used for the said reaction can be used independently, or can be used as a mixed solvent of arbitrary ratio.

The amount of the solvent used for the reaction may be any range as long as stirring is possible, but preferably, the range of 0.1L to 10L can be exemplified with respect to 1 mol of Sym-N-substituted-5-halo-triindole of the raw material. have.

Although the reaction temperature of the said reaction will not be restrict | limited especially if it is a range in which reaction advances, Preferably, it can illustrate the reflux temperature of 40 degreeC-the solvent used. In addition, the reaction time of the said reaction is although it does not restrict | limit especially, 0.5 to 148 hours can be illustrated.

This invention [5] is a 2nd process of said invention [4].

This invention [6] is a 1st process of said this invention [4].

The present invention [7] is a Sym-triindole derivative represented by the general formula (10) by reacting a Sym-triindole derivative represented by the general formula (8) with a methylene compound represented by the general formula (9). It is a manufacturing process.

R <_8> in the methylene compound represented by General formula (9) used for the said reaction represents a hydrogen atom or a cyano group, R <_9> is a cyano group; For example, carboxylic acid groups, such as carboxylic acid, sodium carboxylate, potassium carboxylate, lithium carbonate, pyridinium carboxylate; For example, C1-C6 alkoxycarbonyl groups, such as methoxycarbonyl and ethoxycarbonyl; Aryloxycarbonyl groups such as phenoxycarbonyl group; Aryl groups, such as a phenyl group, a naphthyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidine group, 4-pyrimidine group, and a triazine group; For example, the 2-nitro group, a 3-nitro phenyl, 4-nitrophenyl group, a 4-formyl-phenyl group, represents an 4-cyano-phenyl group, a substituted aryl, such as 6-methyl-2-pyridine group, R ₉ In the case of a heterocycle in which a substituted aryl group contains nitrogen as a binary atom such as pyridine, the salt thereof is also included.

Therefore, as a methylene compound represented by General formula (9) which can be used for the said reaction, for example, acetonitrile, malononitrile, methyl acetate, ethyl acetate, cyanoacetic acid, methyl cyanoacetate, ethyl cyanoacetate , Cyanoacetic acid phenyl, cyanoacetic acid (4-nitrophenyl), 2-cyanomethylpyridine, 3-cyanomethylpyridine, 4-cyanomethylpyridine, 2-cyanomethylpyridine, benzyl cyanide, 4- Nitrobenzyl anide etc. can be illustrated.

If the molar ratio of the methylene compound represented by the general formula (9) used in the reaction is not inhibited, the reaction proceeds at any molar ratio, but with respect to 1 mole of the Sym-triindole derivative represented by the general formula (8), 0.1-30 mol, Preferably 1-10 mol is preferable.

The reaction is usually carried out using a solvent. As a solvent used for the said reaction, for example, aprotic properties such as dimethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, N, N-dimethylimidazolinone and tetramethylurea Polar solvents; For example, Aromatic hydrocarbons, such as toluene, xylene, and chlorobenzene; For example, Chain or cyclic ether, such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane; For example, acetate esters, such as methyl acetate, ethyl acetate, and butyl acetate; For example, nitriles, such as acetonitrile, can be illustrated. The solvent used for the said reaction can be used independently, or can be used as a mixed solvent of arbitrary ratio.

The amount of solvent used in the reaction may be any range as long as stirring is possible, but preferably 0.1 L to 30 L, preferably 0.5 to 1 mol of the Sym-triindole derivative represented by the general formula (8) of the raw material. L-10L can be illustrated.

Although the reaction temperature of the said reaction may be any temperature as long as reaction advances, Preferably it is the range of -20 degreeC-the reflux temperature of the solvent to be used.

Although the reaction time of the said reaction is not specifically limited, Preferably, the range of 1 hour-48 hours can be illustrated.

This invention [8] is a Sym-vinyl triindole derivative represented by General formula (11).

R <_8> in General formula (11) represents a hydrogen atom or a cyano group, R <_9> is a cyano group; For example, carboxylic acid groups, such as carboxylic acid, sodium carboxylate, potassium carboxylate, lithium carbonate, pyridinium carboxylate; For example, C1-C6 alkoxycarbonyl groups, such as methoxycarbonyl and ethoxycarbonyl; Arylcarbonyl groups such as phenoxycarbonyl; Aryl groups, such as a phenyl group, a naphthyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidine group, 4-pyrimidine group, and a triazine group; For example, substituted aryl groups, such as 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 4-formylphenyl group, 4-cyanophenyl group, 6-methyl- 2-pyridine group, are shown.

Therefore, the compound listed in Table 3 can be illustrated as a compound of this invention.

[Formula 37]

TABLE 3

In the present invention [9], a oxyindole compound represented by the general formula (12) is reacted with phosphorus oxyhalide to obtain a Sym-halo-triindole derivative represented by the general formula (13) (first step), and butyllithium Reacting with a formylating agent in the presence of to form a Sym-formyltriindole derivative represented by the general formula (14) (second step), and then reacting with the methylene compound represented by the general formula (9). It is a manufacturing method of the Sym- triindole derivative represented by General formula (11) characterized by (3rd process).

First, reaction of the oxyindole and the phosphorus oxyhalogenated which is the 1st process of this invention is demonstrated.

First, the oxyindole compound represented by General formula (12) used as a raw material is demonstrated.

R <_10> in General formula (12) is linear or branched, for example, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, iso-propyl group, 2-ethylhexyl group, etc. C2-C12 alkyl group; Linear or branched C2 to C12 haloalkyl groups such as chloroethyl group, dichloroethyl group and trifluoroethyl group.

Therefore, as an oxyindole compound represented by General formula (12) which can be used for this invention, N-ethyl-4-bromooxyindole, N-ethyl-5-bromooxyindole, N-ethyl-6-bro Morphoxyindole, N-ethyl-7-bromooxyindole, N- (n-propyl) -5-bromooxyindole, N- (n-butyl) -5-bromooxyindole, N- (n- Pentyl) -5-bromooxyindole, N- (n-hexyl) -5-bromooxyindole, N- (iso-propyl) -5-bromooxyindole, N- (2-ethylhexyl) -5 -Bromooxyindole etc. can be illustrated.

Oxyindole used in the present invention is known, but can be produced by a method of reacting the corresponding aniline with chloroacetyl chloride in the presence of aluminum chloride.

The molar ratio of oxyindole and phosphorus oxyhalogenation used for the raw material may be any molar ratio as long as stirring is possible. Preferably, the molar ratio of 0.5L to 30L, preferably 1L to 10L per mole of oxyindole of the raw material is preferred. It can be illustrated.

Examples of phosphorus oxyhalogenated phosphorus include oxychloride, oxybromide, and the like, and usually phosphorus oxychloride is preferably used.

Although the reaction temperature of the said reaction will not be specifically limited if it is the temperature which reaction advances, Preferably, the range of reflux temperature can be illustrated from 80 degreeC.

Although the reaction time of the said reaction is not specifically limited, Preferably it can illustrate from 1 hour to 48 hours.

Next, formylation of the second step will be described.

The second process of the present invention reacts the Sym-formyltriindole represented by the general formula (14) by reacting the Sym-halo-indole represented by the general formula (13) with a formylating agent in the presence of butyllithium. It is a process of manufacturing.

Examples of the formylating agent used in the present invention include dimethylformamide, diethylformamide, N-formylpiperidine, N-formylpyrrolidine and the like, but preferably dimethylformamide, N -Formyl piperidine is good. The molar ratio of the formylating agent and the Sym-halo-triindole derivative represented by the general formula (13) of the raw material proceeds in any range unless the reaction is inhibited, but the Sym-halo-triindole represented by the general formula (13) 3-30 mol, Preferably 3-9 mol can be illustrated with respect to 1 mol of derivatives.

This process uses butyllithium at the same time. The molar ratio of butyllithium used in this step is reacted at any molar ratio without inhibiting the reaction, but is 3 to 15 moles, preferably 3 to 1 mole of the Sym-halo-triindole derivative represented by the general formula (13). -6 mol can be illustrated.

This process is generally performed using a solvent. As a solvent used at this process, aromatic hydrocarbons, such as toluene and xylene, chain or cyclic ethers, such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, hexamethylphosphoric triamide ( HMPA) and the like can be exemplified, but tetrahydrofuran (THF) is preferable. The solvent used for the said reaction can be used independently, or can be used as a mixed solvent of arbitrary ratio.

The amount of the solvent used for the reaction may be any range as long as stirring is possible, but preferably, the range of 0.1L to 10L can be exemplified with respect to 1 mol of the Sym-halo-triindole derivative of the raw material.

The reaction temperature of the reaction is not particularly limited as long as it is a range in which the reaction proceeds. Preferably, it is -100 ° C to reflux temperature of the solvent to be used, and preferably -78 ° C to 30 ° C.

In addition, the reaction time of the said reaction is although it does not specifically limit, 0.5 to 48 hours can be illustrated.

The 3rd process reacts the Sym-formyl triindole derivative represented by General formula (14) obtained by the 2nd process, and the methylene compound represented by General formula (9), and is represented by General formula (11). Process for the preparation of derivatives.

R <_8> in the methylene compound represented by General formula (9) used for the said reaction represents a hydrogen atom or a cyano group, R <_9> is a cyano group; For example, carboxylic acid groups, such as carboxylic acid, sodium carboxylate, potassium carboxylate, lithium carbonate, pyridinium carboxylate; For example, C1-C6 alkoxycarbonyl groups, such as a methoxycarbonyl group and an ethoxycarbonyl group; Aryloxycarbonyl groups such as phenoxycarbonyl group; Phenyl, naphthyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidine, 4-pyrimidine, triazine, pyrazolyl, triazolyl, quinolinyl, indolyl, Isoindolyl group, thienyl group, benzothienyl group, furyl group, benzofuryl group, thiazolyl group, benzothiazolyl group, oxazolyl group, isoxoxazolyl group, benzooxazolyl group, thiadiazolyl group, benzothiadia Aryl groups, such as an aromatic heterocyclic group of single or condensed ring which has nitrogen, oxygen, and sulfur as a binary atom, such as a sleepy group; For example, substituted aryl groups, such as 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 4-formylphenyl group, 4-cyanophenyl group, and 6-methyl- 2-pyridine group, are shown.

Therefore, as a methylene compound represented by General formula (9) which can be used for the said reaction, acetonitrile, malononitrile, methyl acetate, ethyl acetate, cyanoacetic acid, methyl cyanoacetate, ethyl cyanoacetate, cyanoacetic acid Phenyl, cyanoacetic acid (4-nitrophenyl), 2-cyanomethylpyridine, 3-cyanomethylpyridine, 4-cyanomethylpyridine, 2-cyanomethylpyrimidine, benzyl cyanide, 4-nitrobenzylcia Need, etc. can be illustrated. If the molar ratio of the methylene compound represented by the general formula (9) used in the reaction is not inhibited, the reaction proceeds at any molar ratio to 1 mole of the Sym-formyltriindole derivative represented by the general formula (14). 0.1-30 mol, Preferably 1-10 mol is preferable.

The reaction is usually carried out using a solvent. As a solvent used for the said reaction, Aprotic polar solvents, such as dimethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, N, N- dimethyl imidazolinone, and tetramethylurea; For example, aromatic hydrocarbons, such as toluene, xylene, and chlorobenzene: Chain or cyclic ethers, such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane; For example, acetate esters, such as methyl acetate, ethyl acetate, and butyl acetate; For example, nitriles, such as acetonitrile, can be illustrated.

The solvent used for the said reaction can be used independently, or can be used as a mixed solvent of arbitrary ratio.

The amount of the solvent used for the reaction may be any range as long as stirring is possible, but is preferably 0.1 L to 30 L, preferably 1 mol of the Sym-formyl triindole derivative represented by the general formula (14) of the raw material. Can illustrate 0.5L-10L.

Although the reaction temperature of the said reaction may be any temperature as long as reaction advances, Preferably it is the range of -20 degreeC-the reflux temperature of the solvent to be used.

Although the reaction time of the said reaction is not specifically limited, Preferably, the range of 1 hour-48 hours can be illustrated.

This invention [10] is demonstrated. This invention is a 3rd process of said this invention [9].

This invention [11] is demonstrated. This invention is the 2nd process of said this invention [9].

This invention [12] is demonstrated. The present invention is a Sym-triindole derivative represented by the general formula (15). In the formula, R ₁₀ represents the same meaning as described above, and R ₁₁ is an aryl group such as a phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, or 2-pyrimidine group; For example, substituted aryl groups, such as 4-nitrophenyl group, 4-cyanophenyl group, and 4- (methoxycarbonyl) phenyl group, can be illustrated.

Therefore, as a compound of this invention, the compound listed in Table 4 can be illustrated.

[Formula 38]

TABLE 4

This invention [13] is demonstrated.

The present invention is a method for producing a Sym-triindole derivative represented by Formula (15) by reacting a Sym-halo-triindole derivative represented by Formula (13) with an acetylene derivative represented by Formula (16). to be.

R <_11> in General formula (16) used for the said reaction is aryl groups, such as a phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, and 2-pyrimidine group; For example, substituted aryl groups, such as 4-nitrophenyl group, 4-cyanophenyl group, and 4- (methoxycarbonyl) phenyl group, can be illustrated, and R <_12> represents a hydrogen atom or a trimethylsilyl group.

Therefore, as an acetylene derivative represented by General formula (16) used for the said reaction, phenyl acetylene, 1-phenyl- 2-trimethyl silyl acetylene, (pyridin- 2-yl) acetylene, (pyridin- 3-yl) acetylene, (Pyridin-4-yl) acetylene, (4-cyanophenyl) acetylene, 1- (pyridin-4-yl) -2-trimethylsilylacetylene, etc. can be illustrated.

The molar ratio of the Sym-halo-triindole derivative represented by the general formula (13) and the acetylene derivative represented by the general formula (16) in the reaction proceeds at any molar ratio, but preferably, the general formula (13) 3-10 mol of the acetylene derivative represented by General formula (16) is good with respect to 1 mol of Sym-halo- triindole derivatives represented by

The reaction is generally carried out using a solvent. As a solvent which can be used for the said reaction, For example, aromatic hydrocarbons, such as toluene, xylene, chlorobenzene; For example, aliphatic halogenated hydrocarbons, such as dichloromethane, chloroform; Aprotic polar solvents such as dimethylformamide, diethylformamide, N-methylpyrrolidone and dimethylacetamide; Chain or cyclic ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane; Alcohols such as methanol and ethanol; Polyethylene glycols such as PEG-400; Nitriles, such as acetonitrile; For example, Nitrogen bases, such as pyrrolidine, triethylamine, and pyridine; Water and the like. The solvent used for the said reaction can be used independently, or can be used as a mixed solvent of arbitrary ratio.

The amount of the solvent used in the reaction may be any range as long as stirring is possible, but preferably 0.1 to 20 L with respect to 1 mole of the Sym-halo-triindole derivative represented by the general formula (13) of the raw material.

Although the reaction temperature of the said reaction may be any temperature as long as reaction advances, Preferably it is the range of 20 degreeC-the reflux temperature of the solvent to be used.

Although the reaction time of the said reaction is not specifically limited, Preferably, the range of 1 hour-48 hours can be illustrated.

This invention [14] is demonstrated. This invention is the 1st process of said this invention [9].

FIG. 1 is a diagram showing a light absorption spectrum of a visible region from a visible region of Sym-N- (n-hexyl) -5- (4-formylphenyl) triindole (Formula 36).

2 is a diagram showing a fluorescence spectrum of Sym-N- (n-hexyl) -5- (4-formylphenyl) triindole (formula 36) in a dichloromethane solution state.

3 is a diagram showing a fluorescence spectrum of Sym-N- (n-hexyl) -5- (4-formylphenyl) triindole (formula 36) in a solid state.

Next, although the Example demonstrates the manufacturing method of the compound of this invention concretely, this invention is not limited by these Examples.

Example  One : Sym -N- (n- Hexyl ) -5- Bromotriindole  Produce

Into a 500 ml three-necked flask equipped with a magnet stirrer, a reflux condenser and a thermometer, 40 g of N- (n-hexyl) -5-bromooxyindole and 240 ml of phosphorus oxychloride were heated and refluxed for 8 hours. After the reaction was completed, phosphorus oxychloride was recovered under reduced pressure. To the residue was added water and an aqueous sodium hydroxide solution under cooling. The produced crystal | crystallization was filtered, melt | dissolved in 300 ml of toluene, and heat filtered, and the insoluble matter was removed. The toluene layer was concentrated after washing with water, and the resulting residue was recrystallized (toluene: ethyl acetate = 1: 9) to obtain 10.9 g of Sym-N- (n-hexyl) -5-bromotriindole. Yield 29%.

Melting Point: 205-207 ° C

FAB-Mass (NBA, Positive); ((M + H) ⁺ ) = 835

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.84 (t, J = 6.6 Hz, 9H), 1.20-1.41 (m, 18H), 1.88-2.20 (br, 6H), 4.59 (t, J = 8.1Hz, 6H), 7.41 (t, J = 8.7Hz, 3H), 7.52 (dd, J = 1.5,8.7Hz, 3H), 8.21 (d, J = 1.5Hz, 3H)

Example  2 : Sym -N- (n- Hexyl ) -5- Of phenyltriindole  Produce

In an argon atmosphere, 165 mg of Sym-N- (n-hexyl) -5-bromotriindole and tetrakistriphenylphosphine palladium (0) 35 mg in a 50 ml three-necked flask equipped with a magnet stirrer, reflux cooler and thermometer 20 ml of toluene was added. To this, a 5 ml solution of 109 mg of phenylboronic acid and 10 ml of saturated sodium bicarbonate water were added, and the mixture was heated to reflux for 5 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered. To the obtained filtrate, 50 ml of ethyl acetate and 30 ml of saturated saline were added and separated. The ethyl acetate layer was concentrated, silica gel column chromatography separation (chloroform) was performed to obtain 39 mg of Sym-N- (n-hexyl) -5-phenyltriindole. Yield 23.8%.

FAB-Mass (NBA, Positive); ((M + H) ⁺ ) = 826

¹ H-NMR (270 MHz, CDCl ₃ ), δ (ppm); 0.74 (t, J = 7.1 Hz, 9H), 1.10-1.25 (m, 18H), 2.00-2.10 (br, 6H), 4.96 (t, J = 7.9 Hz, 6H), 7.30-7.41 (m, 3H), 7.48-7.55 (m, 6H), 7.64-7.78 (m, 12H), 8.49 (s, 3H)

Example  3: Sym -N- (n- Hexyl ) -5- (4- Formylphenyl ) Triindole  Produce

Instead of the phenylboronic acid of Example 2, 35 mg of Sym-N- (n-hexyl) -5- (4-formylphenyl) triindole was obtained when 150 mg of 4-formylphenylboronic acid was used. Yield 19.3%.

Melting point; 245 ~ 257 ℃

FAB-Mass (NBA, Positive); ((M + H) ⁺ ) = 910

¹ H-NMR (270 MHz, CDCl ₃ ), δ (ppm); 0.73 (t, J = 7.1 Hz, 9H), 1.00-1.30 (m, 18H), 2.00-2.20 (br, 6H), 4.98 (t, J = 8.1Hz, 6H), 7.74 (s, 6H), 7.91 (d, J = 8.2Hz, 6H), 8.03 (d, J = 8.6Hz), 8.54 (s, 3H), 10.10 (s, 3H)

Example  4 : Sym -N- (n- Hexyl ) -5- (4- Of ethoxycarbonylphenyl) triindole  Produce

Instead of the phenylboronic acid of Example 2, 247 mg of ethyl 4- (4,4,5,6-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was used. 78 mg of N- (n-hexyl) -5- (4-ethoxycarbonylphenyl) triindole was obtained. Yield 37.7%.

Melting Point: 203-213 ° C

FAB-Mass (NBA, Positive); ((M + H) ⁺ ] = 1042

¹ H-NMR (270 MHz, CDCl ₃ ), δ (ppm); 0.74 (t, J = 7.1 Hz, 6H), 1.02-1.28 (m, 18H), 1.45 (t, J = 6.9, 7.2 Hz, 9H) , 2.00-2.18 (br, 6H), 4.44 (q, J = 6.9,7.2Hz, 6H), 4.92 (t, J = 7.9Hz, 6H), 7.68-7.74 (m, 6H), 7.80 (d, J = 8.2 Hz, 6H), 8.19 (d, J = 8.2 Hz, 6H), 8.50 (s, 3H)

Example  5: Sym -N- (n- Hexyl ) -5- (4- Cyanophenyl } Triindole  Produce

Instead of the phenylboronic acid of Example 2, Sym-N was used with 206 mg of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzonitrile. 21.5 mg of-(n-hexyl) -5- (4-cyanophenyl) triindole was obtained. Yield 11.9%.

Melting point; 297 ~ 303 ℃

FAB-Mass (NBA, Postive); ((M + H) ⁺ ] = 901

¹ H-NMR (270 MHz, CDCl ₃ ), δ (ppm); 0.74 (t, J = 7.1 Hz, 9H), 1.05-1.25 (m, 18H), 1.98-2.11 (br, 6H), 4.94 (t, J = 7.5Hz, 6H), 7.69 (d, J = 8.1Hz, 3H), 7.73 (d, J = 8.4Hz, 3H), 7.79 (d, J = 8.7Hz, 6H), 7.83 (d, J = 8.6 Hz, 6H), 8.46 (s, 3H)

Example  6: Sym -N- (n- Hexyl ) -5- (4- (2,2- Dicyano vinyl ) Phenyl ) Triindole  Produce

Under argon atmosphere, 50 ml of Sym-N- (n-hexyl) -5- (4-formylphenyl) triindole 50 mg, malononitrile 16 mg, THF in a 50 ml three-necked flask equipped with a magnet stirrer, reflux cooler and thermometer 5.5 ml was added. 0.165 mg of acetic acid and 2.3 mg of pyrrolidine were added thereto, followed by stirring at room temperature for 4 hours. After completion of the reaction, the residue was concentrated and silica gel column chromatography was separated (chloroform) to give 25 mg of Sym-N- (n-hexyl) -5- (4- (2,2-dicyanovinyl) phenyl) triindole. Got it. Yield 43.2%.

Melting Point: 281 ~ 291 ℃

FAB-Mass (NBA, Positive); ((M + H) ⁺ ] = 1054

Example  7: Sym -N- (n- Hexyl ) -5- Methyltriindole  Produce

Into a 100 ml three-necked flask equipped with a magnet stirrer, a reflux condenser and a thermometer, 7.60 g of N- (n-hexyl) -5-methyloxyindole and 60 ml of phosphorus oxychloride were added and reacted at 100 ° C for 11 hours. After the reaction was completed, phosphorus oxychloride was recovered, and water was added to neutralize with sodium hydroxide. The precipitated crystals were dissolved in 250 ml of toluene after filtration. The toluene layer was filtered off with insoluble materials, washed with water, and dried over sodium sulfate. The toluene layer was concentrated, and then recrystallized (toluene-ethyl acetate = 1: 9) to give 2.16 g of Sym-N- (n-hexyl) -5-methyltriindole. Yield 31%.

Melting Point: 160 ℃

EI-Mass; (M ⁺ ) = 639

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.83 (t, J = 6.6 Hz, 9H), 1.20-1.45 (m, 18H), 2.03 (quint, J = 7.8 Hz, 6H), 2.61 (s.9H), 4.83 (t, J = 8.1 Hz, 6H), 7.25 (bd, J = 8.4 Hz, 3H), 7.50 (d, J = 8.4 Hz, 3H), 8.06 (bs, 3H)

Example  8 : Sym -N- (n- Hexyl ) -5- Formyltriindole  Produce

Under a nitrogen stream, 1.5 g of Sym-N- (n-hexyl) -5-bromotriindole and 180 ml of tetrahydrofuran (THF) were placed in a 300 ml three-necked flask equipped with a magnet stirrer, a reflux cooler and a thermometer. And cooled to -78 ° C. 6.9 ml of 1.57 M-normal butyllithium was slowly dripped here, and it reacted at the same temperature for 1 hour. Then, 1.2 g of N-formyl piperidine was slowly added and reacted at -78 degreeC for 1 hour. The solution was heated to 0 ° C., hydrolyzed by adding dilute hydrochloric acid, and then extracted with toluene. The toluene layer was dried over sodium sulfate, and then concentrated and recrystallized (tetrahydrofuran (THF)) to obtain 1.01 g of Sym-N- (n-hexyl) -5-formyltriindole. Yield 82%

Melting Point: 185-187 ℃

FAB-Mass (NBA, Positive); (M ⁺ ) = 681

IR (KBr, cm- ¹ ); 1687

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.80 (t, J = 7.2 Hz, 9H), 1.20-1.40 (m, 18H), 2.03 (br, 6H), 4.93 (t, J = 7.8Hz, 6H), 7.72 (d, J = 8.7Hz, 3H), 8.02 (dd, J = 0.9,8.4Hz, 3H), 8.77 (d, J = 1.2Hz, 3H), 10.17 (5,3H)

Elemental analysis (Calcd for C ₄₅ H ₅₁ N ₃ O ₃ ) (%); Theory: C79.26, H7.54, N6.16; Found: C79.20, H7.49, N6.19

Example  9: Sym -N- (n- Hexyl ) -5- (2,2- Dicyano vinyl ) Triindole  Produce

In a 50 ml three-necked flask equipped with a magnet stirrer, a reflux condenser and a thermometer, 1.00 g of Sym-N- (n-hexyl) -5-formyltriindole, 0.437 g of malononitrile, 62.4 mg of piperidine, acetic acid 4.40 mg and 10 ml of tetrahydrofuran (THF) were added and reacted at 50 degreeC for 3 hours. After the reaction was completed, the solvent was distilled off, and the obtained residue was recrystallized (tetrahydrofuran (THF)), and 0.681 g of Sym-N- (n-hexyl) -5- (2,2-dicyanovinyl) triindole was added. Got it. Yield 56%.

Melting point; 254-258 ℃

FAB-Mass (NBA, Positive); ((M + H) ⁺ ) = 826

IR (KBr, cm ⁻¹ ); 2223

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.96 (t, J = 7.2 Hz, 9H,), 1.05-1.30 (m, 18H), 1.82 (br, 6H), 5.09 (t, J = 7.2 Hz, 6H), 7.79 (d, J = 8.7 Hz, 3H), 7.94 (s, 3H), 7.97 (dd, J = 1.0, 8.7 Hz, 3H), 8.95 (d, J = 1.0 Hz, 3H )

Elemental analysis; Calcd for C ₅₄ H ₅₁ N ₉ (%); Theory C78.52, H6.22, N15.26; Found C78.30, H6.26, N15.16

Example  10: Sym -N- (n- Hexyl )-(2- Cyano -2- Ethoxycarbonylvinyl ) Triindole  Produce

In a 50 ml three-necked flask equipped with a magnet stirrer, a reflux cooler and a thermometer, 100 mg of Sym-N- (n-hexyl) -5-formyltriindole, 74.8 mg of ethyl cyanoacetate, 6.3 mg of piperidine and tetra 15 ml of hydrofuran (THF) was added and reacted at 50 ° C for 12 hours. After the completion of the reaction, the solvent was distilled off and the residue was recrystallized (tetrahydrofuran (THF)) to obtain Sym-N- (n-hexyl)-(2-cyano-2-ethoxycarbonylvinyl) triindole 99.5 mg was obtained. Yield 70%.

Melting Point: 145-153 ℃

FAB-Mass (NBA, Positive); ((M + H) ⁺ ] = 967

IR (KBr, cm ⁻¹ ); 1590

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.68 (t, J = 7.2 Hz, 9H), 1.05-1.18 (m, 18H), 1.45 (t, J = 7.2 Hz, 9H), 1.78 -1.91 ((bs, 6H), 4.44 (q, J = 7.2Hz, 6H), 5.10 (t, J = 8.1Hz, 6H), 7.76 (d, J = 8.7z, 3H), 8.13 (dd, J = 1.0,8.7Hz, 3H), 8.49 (s, 3H), 8.99 (d, J = 1.0Hz, 3H)

Example  11: Sym -N- (n- Hexyl )-[2- Cyano -2- (4- Nitrophenylvinyl ] Triindole  Produce

In a 50 ml three-necked flask equipped with a magnet stirrer, reflux cooler, thermometer, 100 mg of Sym-N- (n-hexyl) -5-formyltriindole, 107 mg of 4-nitrobenzyl cyanide, 6.3 mg of piperidine and 15 ml of tetrahydrofuran (THF) was added and reacted at 50 degreeC for 12 hours. After completion of the reaction, the precipitated crystals were filtered to obtain 117 mg of Sym-N- (n-hexyl)-[2-cyano-2- (4-nitrophenyl) vinyl] triindole.

Melting Point: 300 ℃ or higher

FAB-Mass (NBA, Positive); ((M + H) ⁺ ] = 1114

lR (KBr, cm ⁻¹ ); 2212, 1340

Example 12; Preparation of Sym-N- (n-hexyl)-[2-cyano-2- (4-pyridyl) vinyl] triindole

In a 50 ml three-necked flask equipped with a magnet stirrer, a reflux cooler and a thermometer, 100 mg of Sym-N-hexyl) -5-formyltriindole, 120 mg of 4-cyanomethylpyridine, 6.3 mg of piperidine and tetrahydrofuran 15 ml of (THF) was added and reacted at 50 ° C for 4 hours. After the reaction was completed, silica gel column chromatography was performed to obtain 131 mg of Sym-N- (n-hexyl)-[2-cyano-2- (4-pyridyl) vinyl] triindole. Yield 91%

Melting Point: 255-260 ℃

FAB-Mass (NBA, Positive); ((M + H) ⁺ ] = 983

IR (KBr, cm ⁻¹ ); 2210

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.64 (t, J = 7.2 Hz, 9H), 0.90-1.14 (m, 18H), 1.82 (br, 6H), 4.81 (t, J = 7.2Hz, 6H), 7.52 (d, J = 8.7Hz, 3H), 7.59-7.61 (m, 6H), 7.82 (s, 3H), 7.96 (dd, J = 1.0,8.7Hz.3H), 8.63 ( bs, 3H), 8.11-8.73 (m, 6H)

Example  13: Sym -N- (2- Ethylhexyl ) -5- Bromotriindole  Produce

Into a 100 ml three-necked flask equipped with a magnet stirrer, a reflux condenser and a thermometer, 5.0 g of N- (2-ethylhexyl) -5-bromooxyindole and 30 ml of phosphorus oxychloride were added and reacted at 100 ° C for 11 hours. . After the reaction was completed, phosphorus oxychloride was recovered under reduced pressure, and water and sodium hydroxide were added to the residue and neutralized. Thereafter, the mixture was extracted with toluene, the toluene layer was concentrated and silica gel column chromatography was separated to obtain 1.11 g of Sym-N- (2-ethylhexyl) -5-bromotriindole. Yield 24%.

EI-MS (M ⁺ ): 918

Melting Point: 161 ℃

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.26-0.33 (m, 9H), 0.56-0.65 (m, 9H), 0.74-1.04 (m, 24H), 1.61-1.72 (br, 3H ), 4.07 (d, J = 7.2 Hz, 6H), 7.42 (d, J = 8.7 Hz, 3H), 7.58 (dd, J = 1.5, 8.7 Hz, 3H), 7.75 (bs, 3H)

Example 14; Preparation of Sym-N- (2-ethylhexyl) -5-formyltriindole

Under a nitrogen stream, 1.1 g of Sym-N- (2-ethylhexyl) -5-bromotriindole and 50 ml of tetrahydrofuran (THF) were placed in a 100 ml three-necked flask equipped with a magnet stirrer, a reflux cooler and a thermometer. , Cooled to -78 ° C. Here, 4.2 ml of 1.57 M-normal butyllithium was slowly added dropwise. After aging at the same temperature for 1 hour, 0.74 g of N-formylpiperidine was slowly added dropwise, and further reacted at -78 ° C for 1 hour. Thereafter, the mixture was elevated to 0 ° C, hydrolyzed by adding dilute hydrochloric acid, and then extracted with toluene. The toluene layer was concentrated and then subjected to silica gel chromatography separation. 0.80 g of Sym-N- (2-ethylhexyl) -5-formyltriindole was obtained. Yield 87%.

Melting Point: 243 ℃

FAB-Mass (NBA, Positive); (M ⁺ ) = 765

IR (KBr, cm ⁻¹ ); 1684

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.33-0.39 (m, 9H), 0.52-0.60 (m, 9H), 0.61-0.96 (m, 24H), 1.74-1.88 (hr, 3H ), 4.67 (d, J = 6.3 Hz, 6H), 7.62 (d, J = 8.4 Hz, 3H), 8.06 (dd, J = 1.2, 8.4 Hz, 3H), 8.51 (bs, 3H), 10.26 (s , 3H)

Example  15; Sym -N- (2- Ethylhexyl ) -5- (2,2- Dicyano vinyl ) Triindole  Produce

In a 500 ml three-necked flask equipped with a magnet stirrer, a reflux condenser, a thermometer, 0.80 g of Sym-N- (2-ethylhexyl) -5-formyltriindole, 0.31 g of malononitrile, 62.4 mg of piperidine and 150 ml of tetrahydrofuran (THF) was put and it reacted at 50 degreeC for 3 hours. After completion of the reaction, the residue was concentrated to recrystallization (tetrahydrofuran (THF)) to obtain 0.15 g of Sym-N- (2-ethylhexyl) -5- (2,2-dicyanovinyl) triindole. Yield 16%.

Melting Point: 290 ° C (Decomposition)

FAB-Mass (NBA, Positive); ((M + H) ⁺ ) = 910

IR (KBr, cm ⁻¹ ); 2224

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.43-0.56 (m, 9H), 0.62-0.70 (m, 9H), 0.72-1.11 (m, 24H), 1.86-2.20 (br, 3H ), 4.99-5.60 (m, 6H), 7.76 (d, J = 8.4 Hz, 3H), 7.93 (s, 3H), 9.11 (bs, 3H)

Example  16: Sym -N- (n- Hexyl ) -5- ( Phenylethyl ) Triindole  Produce

Under a nitrogen stream, 100 mg of Sym-N- (n-hexyl) -5-bromotriindole, 8.35 mg of bistriphenylphosphine palladium dichloride, in a 100 ml three-necked flask equipped with a magnet stirrer, a reflux cooler and a thermometer, 2.27 mg of copper iodide (I), 4 ml of triethylamine and 4 ml of toluene were added and reacted at 70 degreeC for 9 hours. After the reaction was completed, the mixture was cooled to room temperature and neutralized with dilute hydrochloric acid. This was extracted with toluene, and the organic layer was washed with water and brine. After the toluene layer was concentrated, silica gel column chromatography was performed to obtain 10 mg of Sym-N- (n-hexyl) -5- (phenylethyl) triindole. Yield 9.3%.

Melting Point: 180-189 ℃

IR (KBr, cm ⁻¹ ); 2927, 1565, 1494

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm); 0.758 (t, J = 7.2 Hz, 9H), 1.15-1.50 (m, 18H), 2.00-2.17 (m, 6H), 4.79-4.87 ( m, 6H), 7.34-7.42 (m, 9H), 7.56-7.66 (m, 12H) 8.418 (s, 3H)

Example 17 : Sym -N- (n- Hexyl ) -5- [2- Cyano -2- (4- Pyridyl )vinyl] Triindole iodide Preparation of Methyl Salt

100 mg (0.10 mmol) of Sym-N- (n-hexyl) -5- [2-cyano-2- (4-pyridyl) vinyl] triindole in a 25 ml reaction flask equipped with magnet stirrer, reflux cooler and thermometer ) And 2 ml of methyl iodide were added and stirred at room temperature for 12 hours. The mixture was concentrated under reduced pressure, and the residue was washed with hexane, toluene, ethyl acetate, and tetrahydrofuran. The crude crystals were dissolved in a small amount of methanol, and recrystallized by adding dichloromethane to give 114 mg of dark brown crystals (yield 81%).

Melting Point: 236-238 ° C

IR (KBr) 2214 cm ^-1

¹ H-NMR (300 MHz, DMSO-d ₆ ), δ (ppm): 0.44 (t, J = 6.9 Hz, 9H), 0.72-0.98 (m, 24H), 1.71 (m, 6H), 4.34 (s, 9H), 5.22 (m, 6H), 8.27 (d, J = 9.3 Hz), 8.39 (d, J = 9.0 Hz, 3H), 8.44 (d, J = 6.6 Hz), 9.01 (s, 3H), 9.04 (d, J = 6.9Hz, 6H), 9.11 (s, 3H)

Example  18: Sym -N- (2- Ethylhexyl ) -5- [2- Cyano -2- (4- Nitrophenyl )vinyl] Triindole  Produce

In a 25 ml reaction flask equipped with magnet stirrer, reflux cooler and thermometer, 200 mg (0.26 mmol) of Sym-N- (2-ethylhexyl) -5-formyltriindole, 254 mg (1.56 mmol) of 4-cyanomethylnitrobenzene ), Piperidine 0.5 ml and tetrahydrofuran 5 ml were added and stirred at 65 ° C for 12 hours. After confirming the disappearance of the raw materials by TLC, the reddish brown crystals precipitated by adding water were filtered off and washed with toluene. The obtained cake was purified by silica gel column chromatography to obtain 20 mg of orange crystals (yield 6%).

Melting Point: 267-272 ℃

IR (KBr) 854, 1340, 2210 cm ^-1

¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm): 0.45-0.54 (m, 9H), 0.60-0.66 (m, 9H), 0.68-1.12 (m, 24H), 1.99 (m, 3H), 5.11 (m, 6H), 7.74 (d, J = 8.4HZ), 7.87-7.96 (m, 12H), 8.35 (d, J = 8.7Hz, 6H), 9.17 (s, 3H)

Elemental analysis; Calcd for C ₇₅ H ₇₅ N ₉ O ₆ (%); Theoretic C75.16, H6.31.N10.52; Found C75.13, H6.31, N10.38

Example  19: Sym -N- (2- Ethylhexyl ) -5- [2- Cyano -2- Hydroxycarbonylvinyl ] Triindole  Produce

371 mg (0.48 mmol) of Sym-N- (2-ethylhexyl) -5-formyltriindole, 618 mg (7.2 mmol) cyanoacetate, ammonium acetate in a 50 ml reaction flask equipped with a magnet stirrer, reflux cooler and thermometer 112 mg (1.44 mmol) and 20 ml of tetrahydrofuran were put, and it stirred at 65 degreeC for 12 hours. Toluene was added to precipitate the yellow cake which was precipitated, and washed with water and toluene. The crude cake was dissolved in tetrahydrofuran, toluene was added and recrystallized to filter the cake. Thereafter, the residue was purified by silica gel column chromatography, and subsequently recrystallized from tetrahydrofuran-toluene to obtain 376 mg of yellow crystals.

FAB-Mass (NBA, Positive) :( M ⁺ ) = 967

Melting Point: 298-301 ℃

IR (KBr) 1716, 2224, 2960 cm ^-1

¹ H-NMR (300 MHz, DMSO-d ₆ ), δ (ppm): 0.32-0.39 (m, 9H), 0.51 (m, 9H), 0.60-0.97 (m, 24H), 1.77 (m, 3H), 4.99 (m, 6H), 8.07 (d, J = 8.7 Hz, 3H), 8.62 (s, 3H), 8.96 (s, 3H), 13.7 (bs, 3H)

Elemental analysis; Calcd for C ₆₀ H ₆₆ N ₆ O ₆ (%); Theoretical C74.51, H6.88, N8.69; Found C74.90, H6.93, N8.27

Example  20: Sym -N- (2- Ethylhexyl ) -5- Cyanotrianthol  Produce

150 mg (0.20 mmol) of Sym-N- (2-ethylhexyl) -5-formyltriindole, 50 mg of hydroxylamine hydrochloride, 60 mg of sodium acetate, methanol in a 200 ml reaction flask equipped with a magnet stirrer, reflux cooler and hygrometer 50 ml and toluene 50 ml were put and stirred at room temperature for 12 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained crystal was washed with water and dried.

The crystal obtained previously, 100 ml of toluene and 1 g of acetic anhydride were put into the 200 ml reaction flask provided with the magnet stirrer, the reflux cooler, and the thermometer, and it heated and refluxed for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, and 100 ml of water was added to the solution. The toluene layer was concentrated, and the obtained residue was separated by column chromatography to obtain 14 mg of Sym-N- (2-ethylhexyl) -5-cyanotriindole. (Yield 9.2%)

FAB-Mass (NBA, Positive): ((M + H) ⁺ ] = 757

Melting Point: 248 ℃

IR (KBr) 2219 cm ^-1

¹ H-NMR (270 MHz, CDCl ₃ ), δ (ppm): 0.30-0.40 (m, 9H), 0.42-1.05 (m, 33H), 1.60-1.80 (m, 3H), 4.35 (d, J = 7.2 Hz, 6H), 7.75 (d, J = 8.2 Hz, 3H), 7.89 (dd, J = 1 Hz, 8.9 Hz, 3H), 7.93 (s, 3H)

[Industry availability]

The present invention provides a novel substituted Sym-triindole derivative and a method for preparing the same. Substituted Sym-triindole derivatives include various antistatic, antistatic, capacitors, batteries, chemical sensors, display elements, organic EL materials, solar cells, photodiodes, phototransistors, nonlinear materials, photoreflective materials, rust inhibitors, adhesives, fibers It can be widely applied to anti-static paint, electrodeposition paint, plating primer, electric method.

Claims (14)

General formula (1)

(In formula, R <_1> , R <_2> , R <_3> , R <_4> is respectively independently hydrogen, halogen, C1-C6 alkyl group, C1-C6 haloalkyl group, substituted C1-C6 alkyl group, C2-C6 alkenyl group, substituted C2- C6 alkenyl group, C2-C6 alkynyl group, substituted C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, aryloxy group, amino group, monosubstituted amino group, disubstituted amino group, acylamino group, mercapto group, C1- C6 alkylsulphenyl group, C1-C6 haloalkylsulphenyl group, arylsulphenyl group, substituted arylsulphenyl group, C1-C6 alkylsulfinyl group, C1-C6 haloalkylsulfinyl group, aralkylsulphenyl group, arylsulfinyl group, substituted arylsulfinyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylsulfonyl group, arylsulfonyl group, substituted arylsulfonyl group, sulfonic acid group (hydroxysulfonyl group), aryl group, substituted aryl group, cyano group, nitro group, formyl group, Acyl group, carboxyl group, C1-C6 alkoxycarbonyl group, carbamoyl group, N-monosubstituted carbamoyl group, N, N-disubstituted carbamoyl group, hydrazonomethyl group (-CH = N-NH ₂ group), N-mono substituted hydrazonomethyl group, N, N-disubstituted hydrazonomethyl group, an oxime methyl group (hydroxyiminomethyl group), C1-C6 alkoxy iminomethyl group, an aryloxy iminomethyl group, R ₅ Represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group, provided that R ₁ , R ₂ , R ₃ , and R ₄ are not all hydrogen at the same time. ) Substituted Sym-triindole derivative, characterized in that. General formula (2)

(In formula, R <_1> , R <_2> , R <_3> , R <_4> is respectively independently hydrogen, halogen, C1-C6 alkyl group, C1-C6 haloalkyl group, substituted C1-C6 alkyl group, C2-C6 alkenyl group, substituted C2- C6 alkenyl group, C2-C6 alkynyl group, substituted C2-C6 alkynyl group, hydroxyl group, C1-C6 alkoxy group, aryloxy group, amino group, monosubstituted amino group, disubstituted amino group, acylamino group, mercapto group, C1- C6 alkylsulphenyl group, C1-C6 haloalkylsulphenyl group, aralkylsulphenyl group, arylsulphenyl group, substituted arylsulphenyl group, C1-C6 alkylsulfinyl group, C1-C6 haloalkylsulfinyl group, arylsulfinyl group, substituted arylsulfinyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylsulfonyl group, arylsulfonyl group, substituted arylsulfonyl group, sulfonic acid group (hydroxysulfonyl group), aryl group, substituted aryl group, cyano group, nitro group, formyl group, Acyl group, carboxyl group, C1-C6 alkoxycarbonyl group, carbamoyl group, N-monosubstituted carbamoyl group, N, N-disubstituted carbamoyl group, hydrazonomethyl group (-CH = N-NH ₂ group), N-mono substituted hydrazonomethyl group, N, N-disubstituted hydrazonomethyl group, an oxime methyl group (hydroxyiminomethyl group), C1-C6 alkoxyiminomethyl group, an aryloxy iminomethyl group, R ₅ Represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, or an aryl C1-C6 alkyl group, provided that R ₁ , R ₂ , R ₃ , and R ₄ are not all hydrogen at the same time. ) The reaction of substituted oxyindole represented by phosphorus oxyhalogenated with the following general formula (1)

(Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ represent the same meanings as above). Method for producing a substituted Sym-triindole derivative represented by. General formula (3)

(Wherein R ₅ represents C2-C12 alkyl group, substituted C2-C12 alkyl group, C2-C12 haloalkyl group, aryl C1-C6 alkyl group, R ₆ represents hydrogen, formyl group, cyano group, C1-C6 alkoxycarbonyl group, dicyano A vinyl group, an aryl group, or a substituted aryl group.) Sym-triindole derivative, characterized in that represented by. General formula (4)

(Wherein R ₅ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, an aryl C1-C6 alkyl group, and X represents a halogen.) N-substituted-5-halo-oxyindole represented by (Wherein R ₅ and X have the same meaning as above). To obtain an N-substituted-5-halo-triindole derivative represented by the following formula (6)

(Wherein R ₇ represents hydrogen, formyl group, cyano group, C1-C6 alkoxycarbonyl group, aryl group or substituted aryl group, and R _a , R _b may each independently have a hydrogen atom, a C1-C6 alkyl group or a substituent) Represents a phenyl group, and R _a and R _b may be bonded to each other to form a ring) Reacting with a boric acid compound represented by the following general formula (7)

(Wherein R ₅ and R ₇ have the same meaning as above). Method for producing a Sym- triindole derivative represented by. General formula (5)

(Wherein R ₅ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, an arylC1-C6 alkyl group, and X represents a halogen.) N-substituted-5-halo-triindole derivatives represented by the following general formula (6)

(Wherein R ₇ represents hydrogen, formyl group, cyano group, C1-C6 alkoxycarbonyl group, aryl group or substituted aryl group, and R _a , R _b may each independently have a hydrogen atom, a C1-C6 alkyl group or a substituent) It may represent a phenyl group, and R _a and R _b may combine to form a ring.) Reacting with a boric acid compound represented by the following general formula (7)

(Wherein R ₅ and R ₇ have the same meaning as above). Method for producing a Sym- triindole derivative represented by. General formula (4)

(Wherein R ₅ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, an aryl C1-C6 alkyl group, and X represents a halogen.) N-substituted-5-halo-oxyindole represented by the following reaction with phosphorus oxyhalogenide, the following general formula (5)

(Wherein R ₅ and X have the same meaning as above). Method for producing an N-substituted-5-halo-triindole derivative represented by General formula (8)

(In formula, R <_5> represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group, and an aryl C1-C6 alkyl group.) Triindole derivatives represented by the following formula (9)

(Wherein R ₈ represents hydrogen or a cyano group, and R ₉ represents a cyano group, a carboxylic acid group, a C1-C6 alkoxycarbonyl group, an aryl group, a substituted aryl group.) Reacting with a methylene compound represented by the following general formula (10)

(Wherein R ₅ , R ₈ and R ₉ represent the same meaning as above). Method for producing a Sym- triindole derivative represented by. General formula (11)

(Wherein R ₈ represents hydrogen or cyano group, R ₉ represents cyano group, carboxylic acid group, C1-C6 alkoxycarbonyl group, aryl group or substituted aryl group, R ₁₀ represents C2-C12 alkyl group, substituted C2-C12 alkyl group) , C2-C12 haloalkyl group or aryl C1-C6 alkyl group.) Sym-triindolevinyl derivative, characterized in that represented by. General formula (12)

(Wherein R ₁₀ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group or an aryl C1-C6 alkyl group, and X represents a halogen.) The oxyindole compound represented by the reaction is reacted with phosphorus oxyhalogenated compound, and the following general formula (13)

(Wherein R ₁₀ and X have the same meaning as above). To obtain a Sym-halo-triindole derivative represented by the following formula, formylated with a formylating agent in the presence of butyllithium,

(Wherein R ₁₀ represents the same meaning as above). To obtain a Sym-formyltriindole derivative represented by the following formula (9)

(Wherein R ₈ represents hydrogen or a cyano group, and R ₉ represents a cyano group, a carboxylic acid group, a C1-C6 alkoxycarbonyl group, an aryl group, a substituted aryl group.) It is made to react with the methylene compound represented by the following general formula (11)

(In formula, R <_8> , R <_9> , R <_10> shows the same meaning as the above.) Method for producing a Sym- triindole derivative represented by. General formula (14)

(Wherein R ₁₀ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group or an aryl C1-C6 alkyl group.) Sym-formyltriindole derivatives represented by the following general formula (9)

(Wherein R ₈ represents hydrogen or a cyano group, and R ₉ represents a cyano group, a carboxylic acid group, a C1-C6 alkoxycarbonyl group, an aryl group, a substituted aryl group.) It is made to react with the methylene compound represented by the following general formula (11)

(In formula, R <_8> , R <_9> , R <_10> shows the same meaning as the above.) Method for producing a Sym- triindole derivative represented by. General formula (13)

(Wherein R ₁₀ represents a C2-C12 alkyl group, a C2-C12 substituted alkyl group, a C2-C12 haloalkyl group or an aryl C1-C6 alkyl group, and X represents a halogen.) To the Sym-halo-triindole derivative represented by the following formula (3), formylation is carried out with a formylating agent in the presence of butyllithium.

(Wherein R ₁₀ represents the same meaning as above). Method for producing a Sym- formyl triindole derivative represented by. General formula (15)

(Wherein R ₁₀ represents a C2-C12 alkyl group, a C2-C12 substituted alkyl group, a C2-C12 haloalkyl group or an aryl C1-C6 alkyl group, and R ₁₁ represents an aryl group or a substituted aryl group.) Sym-triindole derivative, characterized in that represented by. General formula (13)

(Wherein R ₁₀ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group or an aryl C1-C6 alkyl group, and X represents a halogen.) Sym-halo-triindole derivatives represented by the following general formula (16)

(Wherein R ₁₁ represents an aryl group or a substituted aryl group, and R ₁₂ represents hydrogen or a trimethyl silyl group.) Reacting with an acetylene derivative represented by the general formula (15)

(In formula, R <_10> , R <_11> shows the same meaning as the above.) Method for producing a Sym- triindole derivative represented by. General formula (13)

(Wherein R ₁₀ represents a C2-C12 alkyl group, a substituted C2-C12 alkyl group, a C2-C12 haloalkyl group or an aryl C1-C6 alkyl group, and X represents a halogen.) Sym-halo-triindole derivative, characterized in that represented by.

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